PL179980B1 - Composition for giving textiles lower flammability, and for softening a fabric, a textile material treated by said composition, and a method of manufacturing said composition - Google Patents

Abstract

1. A composition adapted to impart flame retardant and fabric softening properties to textile materials, characterized in that it is a stable, 60% aqueous solution of a product obtained by the reactions of: (a) tetrakis(hydroxymethyl)phosphonium chloride (THPC); (b) urea; and (c) a primary amine having 12 to 18 carbon atoms, wherein the molar ratio of a:b:c is in the range of (4 to 1.5):(0.95 to 0.75):(0.25 to 0.05). 5. A method of producing a composition adapted to impart flame retardant and fabric softening properties to textile materials, comprising a stable, 60% aqueous solution of a product obtained by the reactions of: (a) tetrakis(hydroxymethyl)phosphonium chloride (THPC); (b) urea; and (c) a primary amine having 12 to 18 carbon atoms, wherein the molar ratio of a:b:c is in the range (4 to 1.5):(0.95 to 0.75):(0.25 to 0.05), characterized by (i) placing THPC (a) in a vessel and adjusting its pH to about 6.0 by adding an inorganic base; (ii) dissolving urea (b) in the THPC/base solution; (iii) adding amine (c) to the mixture of compounds [(a) + (b)]; (iv) maintaining the mixture [(a) + (b) + (c)] at reflux temperature for 3 to 4 hours to form a condensation product of components (a) and (b); (v) cooling the resulting product; and (vi) there is added thereto a quantity of water sufficient to produce a stable 60% aqueous solution of the product. PL PL

Description

The present invention relates to a composition adapted to impart flame retardant and fabric softening properties to textiles, and to a method of making the composition.

A known method of treating a fabric containing cellulose (e.g. cotton) fibers to reduce flammability is to impregnate the fabric with an aqueous solution of a poly (hydroxyorgano) phosphonium compound, e.g. a tetrakis (hydroxyorgano) phosphonium (THP +) salt. Alternatively, the poly (hydroxyorgano) phosphonium compound may contain a condensation product with a nitrogen-containing compound such as urea. After impregnation, the fabric is dried and then hardened with ammonia to form a hardened, water-insoluble polymer that is mechanically inserted into the fabric fibers. After curing, the polymer is oxidized to convert trivalent phosphorus to pentavalent phosphorus, and the fabric is washed and dried. Fabrics treated as described above and garments made from the fabrics so treated are sold under the trade mark PROBAn by Albright and Wilson Limited.

GB-A-2271787 discloses the addition of one or more protonated and neutralized amines (e.g., amine acetates) to the impregnating solution. It was found

This addition increases the efficiency of introducing the phosphonium compound inside the fibers and improves the homogeneous distribution of the phosphonium compound in the system, which, in turn, has been found to lead to improved flame retardancy and increased hydrophobic properties.

GB-A-2040299 discloses the addition of an inorganic C 1 -C 6 amine tertiary base or base to a THP + compound prior to condensation with urea. However, the above-mentioned GB-A-2040299 does not deal with the problem of the softness (drape) of a textile after treatment with the product of this disclosure.

British Patent Application No. Bg 9412484.9 discloses a method of increased impregnation of a fabric with a THP + compound which improves the flame retardant properties.

It has now been found that adding a THP + salt and a nitrogen-containing organic compound to an aqueous mixture before reacting the components to condense the THP + salt and the nitrogen-containing organic compound, a primary or secondary aliphatic amine with 12 or more carbon atoms, produces a composition that when used for the treatment of textiles according to the above-mentioned PROBAN method, not only imparts to the textiles flame retardant properties, but also improves the softening properties of the fabric.

The composition according to the invention is adapted to impart flame retardant and fabric softening properties to textiles and is characterized in that it constitutes a stable 60% aqueous solution of the product obtained by the reaction of: (a) tetrakis (hydroxymethyl) phosphonium chloride (THPC); (b) urea: and (c) a primary amine of 12 to 18 carbon atoms, where the a: b: c molar ratio is in the range (4 to 1.5) :( 0.95 to 0.75) :( 0.25 to 0.05).

Preferably, compound (c) is n-dodecylamine (C ^^^ NIty) or n-octadecylamine (C ₁₈ H3 ₇ NH ₂ ).

Alternatively, compound (c) may be tallow amine, which is believed to contain n-hexadecylamine (C ₁₆ H _{3 1} NH 2) and n-octadecylamine (C 1 H 2 N H 2).

Preferably, the a: b: c molar ratio may be any of the following:

3.5 0.95 0.05 3 0.95 0.05 2.5 0.95 0.05 2.5 0.9 0.1 2.5 0.75 0.25 2 0.9 0.1 or 1.5 0.95 0.05

The composition of the invention is useful for the impregnation of a textile material consisting essentially of 100% cellulose fibers (e.g. cotton, linen, jute, hessian or regenerated cellulosic material). The material may also contain cotton fibers.

A textile material containing cotton and synthetic fibers is also impregnated with the composition according to the invention.

The synthetic fibers can be polyester, polyamide, acrylic or aramid fibers.

The fabric treated with the composition of the invention comprises 65% cotton fibers and 35% polyester fibers or 75% en cotton fibers and 25% polyester fibers.

The invention also relates to a method of producing a composition adapted to impart flame retardant and fabric softening properties to textiles, constituting a stable 60% aqueous solution of the product obtained by the reaction of: (a) tetrakis (hydroxymethyl) phosphonium chloride (THPC); (b) urea; and (c) a primary amine with 12 to 18 carbon atoms, wherein the a: b: c molar ratio is (4 to 1.5) :( 0.95 to 0.75) :( 0.25 to 0 , 05), which consists in (i) placing THPC (a) in a vessel and adjusting its pH to about 6.0 by adding an inorganic base; (ii) in a THPC solution / dissolution base

Urea (b) is purged; (iii) the amine (c) is added to the mixture of compounds [(a) + (b)]; (iv) keeping the mixture [(a) + (b) + (c)] at reflux for 3 to 4 hours until a condensation product of components (a) and (b) is formed; (v) cooling the obtained product; and (vi) adding an amount of water thereto sufficient to make a stable 60% aqueous solution of the product.

In the process of the invention, the inorganic base used in step (i) may be, for example, sodium hydroxide or potassium hydroxide.

In step (iv) of the process, the mixture may be maintained, for example, at reflux temperature of the ingredients for 3 to 4 hours. This step can be carried out under atmospheric or superatmospheric pressure, eg. About 1.25 · 10 ⁵ Pa.

In step (vi) of the process, an appropriate amount of water can be added to the product to produce a 60% stable solution. While not intending to refer to any particular theory, it is believed that adjusting the pH of the THPC salt to about 6.0 may make the salt more reactive with the nitrogen-containing organic compound. It is also believed that the markedly softer hand (drift) of the treated textile may be due in part to the reduced degree of cross-linking of the THP ⁺ salt condensation product / compound (c) on the material and / or the presence of compound (c) in the chain. It is further believed that treatment of the textiles according to the invention can lead to an improvement in tear resistance and abrasion resistance.

The following examples illustrate the invention:

Example I.

1400 grams of tetrakis (hydroxymethyl) phosphonium chloride (THPC) was added to a two liter resin kettle equipped with a condenser. By adding 75 grams of 50% sodium hydroxide solution, the pH was adjusted to about 6. 132 grams of urea was introduced into the resin kettle and allowed to dissolve with stirring.

38 grams of n-octadecylamine (available as ARMEEN * HTD) was introduced into the kettle and the temperature was raised to reflux. The mixture was kept at this temperature for 3-4 hours until all amine had disappeared. Then heating was stopped and water was added to make a 60% solution.

The molar ratio of THPC: urea: n-octadecylamine was 2.5: 0.95: 0.05.

100% cotton fabric with a grammage of 280 g / m ^{2 was} impregnated with the above liquid in order to obtain PROBAN * with 40% impregnation and processed according to the known PROBAN * process. The finished fabric was dry impregnated with 18.5% condensation product.

The fabric processed with the above liquid was found to contain 2.75% P and 2.38% N and passed the German (a), French (b) and English (c) FR-tests both before and after 40 washing cycles at 93 ° C .

Examples II to VI

The process of Example 1 was repeated, and the amounts and results are shown in Table 1 below:

All fabrics in Examples 2 through VI (above) passed the flame retardant tests listed in Example I.

Notes on Example I:

* the words ARMEEN and PROBAN are trademarks of (a) DIN 66083 s-b (b) NFG 07-184 (c) BS 6 249

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Table 1

Example no (a) THPC (g) 50% KOH (g) (b) Urea (g) (c) Amine (g) Ratio molar (ABC) Dry impregnation (%) Content in processed fabric P (%) N (%) II 1190 60 108 48 * 2.5: 0.75: 0.25 17.6 2.6 2.25 III 1428 75 171 36 * 2: 0.95: 0.25 19 2.77 2.55 IV 1190 60 108 48 * 2.5: 0.9: 01 17.6 2.6 2.25 V 1428 75 162 72 * 2: 0.9: 01 19 2.6 2.44 VI 1190 101 108 18.5+ 2.5: 0.9: 01 - 2.96 2.52

* n-octadecylamine n-dodecylamine

Examples VII to X

The process of Example 1 was repeated, but these examples relate only to the preparation of a flame retardant composition and not to its application to textiles. The quantities are shown in Table 2 (below):

Table 2

Example no (a) THPC (g) 50% KOH (g) (b) Urea (g) (c) Amine (g) Molar ratio (a: b: c) Comments VII 1190 60 95 twenty 3: 0.95: 0.05 VIII 1190 60 71 15 4: 0.95: 0.05 IX 1190 60 81.4 17 3.5: 0.95: 0.05 X 1074 60 171 36 1.5: 0.95: 0.05 A polymeric gel is formed

The fabrics treated with the products of Examples 1 to 6 above showed significantly better fabric grip and stacking compared to the fabrics treated with the formulation of GB-A-2,040,299 described above.

Examples XI to XV

Example 1 was repeated using the molar ratio of THPC: Urea: Amine 3: 0.95: 0.05 at the pressures, temperatures and times shown in Table 3 (below):

Table 3

Example Temperature ° C Pressure Pa 10 ^s Time min. XI 105-108 Atmospheric 180 XII 110 0.5 150 XIII 130 1.25 twenty XIV 130 1.25 twenty XV 130 1.25 twenty

100% wool fabric with a basis weight of 280 g / m ^{2 was} processed using the product described above. The processed fabric was found to have phosphorus and nitrogen content of 3 and 2.5%, respectively, and passed the German, French, English and the new European Pr EN 533 flame retardant test after 40 washes at 93 °.

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Examples XVItoXX

Example 11 was repeated using the fabrics shown in Table 4 (below): The treated fabrics conform to the flame retardant standards of German, French, English and the new European Pr EN 533, after washing required for the durability test.

Table 4

Example Fabric composition% Cotton PET * Building Fabric weight g / m ² XVI 100 0 Diagonal 280 XVII 100 0 Flat 155 XVIII 100 0 (pigment print) Flat 185 XIX 75 25 Diagonal 255 XX 65 35 Diagonal 280

* PET - polyethylene terephthalate

Table 5 below shows the P and N results before and after washing for the durability test. In addition, the fabrics exhibit unusual grip and stacking. In addition, the treated fabrics were hydrophobic.

Table 5

Example P and N content (%) (after finishing) P and N content (%) (after washing) P% N% P% N% XVI 3.05 2.46 2.84 2.26 XVII 4.55 3.65 - _- * XVIII 2.98 2.45 2.10 1.63 XIX 3.02 2.46 3.01 2.24 XX 3.49 2.81 2.97 2.42

In Example 17, the fabric was subjected to 200 extended laundering cycles at 74 ° C with an oxidizing agent-free detergent. The phosphorus content of the fabric after the durability tests was 2.80%, and nitrogen was 2.21%. The fabric has passed BS 5867 Part 2 Type B.

Publishing Department of the UP RP. Circulation of 60 copies

Price PLN 2.00.

Claims (6)

Patent claims A composition adapted to impart flame retardant and fabric softening properties to textiles characterized by being a stable 60% aqueous solution of the product obtained by the reaction of: (a) tetrakis (hydroxymethyl) phosphonium chloride (THPC); (b) urea: and (c) a primary amine of 12 to 18 carbon atoms, where the a: b: c molar ratio is in the range (4 to 1.5) :( 0.95 to 0.75) :( 0.25 to 0.05). 2. A composition according to claim 1 The process of claim 1, wherein it is the reaction product of essentially n-dodecylamine (C ₁₂ H _{2 5 In} N ₂ ) as compound (c). 3. A composition according to p. The compound of claim 1, wherein it is the reaction product of essentially n-octadecylamine (C ₁₈ H3 ₇ NH)) as compound (c). 4. A composition according to p. 3. The method of claim 1, 2 or 3, characterized in that the molar ratio a: b: c is in the range of 3.5: 0.95: 0.05.3: 0.95: 0.05.2.5: 0.95: 0.05, 2.5: 0.9: 0.1, 2.5: 0.75: 0.25.2: 0.9: 0.1 or 1.5: 0.95: 0.05. 5. A method of producing a composition adapted to impart flame retardant and fabric softening properties to textiles, constituting a stable, 60% aqueous solution of the product obtained by the reaction of: (a) tetrakis (hydroxymethyl) phosphonium chloride (THPC); (b) urea; and (c) a primary amine with 12 to 18 carbon atoms, wherein the a: b: c molar ratio is (4 to 1.5) :( 0.95 to 0.75) :( 0.25 to 0 , 05), characterized by (i) placing THPC (a) in the vessel and adjusting its pH to about 6.0 by adding an inorganic base; (ii) the urea (b) is dissolved in the THPC / base solution; (iii) the amine (c) is added to the mixture of compounds [(a) + (b)]; (iv) keeping the mixture [(a) + (b) + (c)] at reflux for 3 to 4 hours until a condensation product of components (a) and (b) is formed; (v) cooling the obtained product; and (vi) adding an amount of water thereto sufficient to make a stable 60% aqueous solution of the product. 6. The method according to p. A process as claimed in claim 5, wherein the inorganic base in step (i) is sodium hydroxide or potassium hydroxide.